US20100040861A1 - Ordered Mesoporous Free-Standing Carbon Films And Form Factors - Google Patents

Ordered Mesoporous Free-Standing Carbon Films And Form Factors Download PDF

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US20100040861A1
US20100040861A1 US12/190,937 US19093708A US2010040861A1 US 20100040861 A1 US20100040861 A1 US 20100040861A1 US 19093708 A US19093708 A US 19093708A US 2010040861 A1 US2010040861 A1 US 2010040861A1
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ordered mesoporous
scaffold
carbon
substrate
mesoporous carbon
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US12/190,937
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William Peter Addiego
Wageesha Senaratne
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Corning Inc
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Corning Inc
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Priority to US12/190,937 priority Critical patent/US20100040861A1/en
Assigned to CORNING INCORPORATED reassignment CORNING INCORPORATED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ADDIEGO, WILLIAM PETER, SENARATNE, WAGEESHA
Priority to JP2011522985A priority patent/JP2011530480A/ja
Priority to EP09789109A priority patent/EP2331481A1/en
Priority to PCT/US2009/004597 priority patent/WO2010019221A1/en
Priority to CN2009801317459A priority patent/CN102203031A/zh
Publication of US20100040861A1 publication Critical patent/US20100040861A1/en
Abandoned legal-status Critical Current

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Definitions

  • the present invention relates to a method of forming free-standing ordered mesoporous carbon films and form factors.
  • the method comprises forming a precursor mixture containing a carbon precursor, at least one surfactant, oil, and water, depositing the precursor mixture onto a substrate, and then drying, cross-linking and heat treating (carbonizing) the carbon precursor to form the carbon film or form factor.
  • the invention also relates to the carbon films and form factors made according to the method.
  • both the macroscale and mesoporous morphology of the films and form factors can be controlled by varying process conditions such as the ratio of carbon precursor: surfactant: oil:water in the precursor mixture, the choice of substrate, and the drying and carbonizing conditions.
  • Ordered mesoporous carbon materials comprise a three-dimensionally ordered and interconnected array of pores that range in size from about 2 to 50 nm.
  • Ordered mesoporous carbons can exhibit BET specific surface areas as high as about 2200 m 2 /g, and typically exhibit excellent thermal stability in inert atmospheres, and strong resistance to attack by acids and bases.
  • the macro geometry, pore geometry and surface chemistry, including the optional incorporation of surface active species can be tailored according to the desired application.
  • Ordered mesoporous carbons can be used in a variety of applications, including water/air purification, gas separation, filtration, catalysis, adsorption, chromatographic separations, capacitive deionization, electrochemical double-layer capacitors, ultracapacitors, and hydrogen storage.
  • free-standing carbon films and form factors comprising ordered mesoporous carbon material can be prepared, for example, by depositing an aqueous precursor mixture comprising a water soluble carbon precursor, a non-ionic surfactant, an oil and water onto a substrate or scaffold, drying and cross-linking the precursor mixture, and heat treating the coated substrate or scaffold. After deposition of the precursor mixture, but before cross-linking of the carbon precursor, self-assembly of the surfactant forms a template for the carbon precursor. After carbonization, the carbon films and form factors comprise ordered domains of mesoscale porosity.
  • Free-standing carbon films having a film thickness ranging from about 100-500 micrometers can be formed using the inventive method.
  • a thin layer of the precursor mixture is deposited onto a first substrate and the as-deposited layer is sandwiched between the first substrate and a second substrate. After drying and cross-linking, the deposited layer is transformed by heating into a free-standing ordered mesoporous carbon film via thermally-induced removal (e.g., pyrolysis) of the solvents and the surfactant-based organic template.
  • thermally-induced removal e.g., pyrolysis
  • Form factors can be prepared using a similar process wherein the precursor mixture is deposited onto a scaffold.
  • Scaffolds can be organic or inorganic, and can include paper, cloth or foam. Once the as-deposited layer is coated onto the scaffold, it is cross-linked and carbonized by heating. Because the scaffold material can be organic, the scaffold can be volatilized during the heat treating step and/or incorporated into the form factor. Because the precursor mixture coats exposed surfaces of the scaffold, the form factor comprises a positive image of the scaffold from which it is derived.
  • Preferred form factors comprise a carbon film-coated reticulated scaffold wherein the carbon film comprises ordered mesoporous carbon.
  • the ordered mesoporous carbon films and form factors according to the invention can be defined by a structure that is ordered at the nanoscale as well as at larger dimensions, e.g., micro-scale ordering corresponding to the substrate or scaffold.
  • the ordered mesoporous carbon films and form factors can be activated.
  • the optional activation which can comprise partially oxidizing surfaces of the carbon material and generally involves a concomitant increase in surface area, can comprise thermal and/or chemical activation.
  • FIG. 1 is a schematic flow chart of a process for forming ordered mesoporous carbon films and form factors
  • FIGS. 2A-2C show scanning electron micrographs for ordered mesoporous carbon form factors prepared using (A) foam, (B) cloth, and (C) paper towel organic scaffolds;
  • FIG. 3 shows plots of X-ray diffraction data for ordered mesoporous carbon (a) powder, (b) carbonized foam, and (c) carbonized cloth;
  • FIG. 4 shows scanning electron micrographs for carbon material prepared using a foam scaffold (comparative).
  • FIG. 5 is series of scanning electron micrographs showing pore orientation in free-standing ordered mesoporous carbon films
  • FIG. 6 is a series of scanning electron micrographs showing (a) a cross sectional view, (b) a bottom surface, and (c) a top surface of ordered mesoporous carbon films on aluminum and Pyrex® brand substrates;
  • FIG. 7 shows X-ray diffraction plots for ordered mesoporous carbon powder and a free-standing film showing reflections for (a) powder, (b) film top surface, and (c) film bottom surface;
  • FIG. 1 is a schematic flow chart depicting examples of processes for forming ordered mesoporous carbon films and form factors.
  • a precursor mixture 100 comprising an aqueous mixture of a carbon precursor, a surfactant, and an oil is coated onto a substrate 120 or scaffold 140 and dried to form a cross-linked coating 150 comprising a mesostructure phase.
  • the mesostructure phase is defined by the self-assembly of an organic template (e.g., liquid crystal phase) that comprises the surfactant.
  • the carbon precursor which is ordered by the organic template, is carbonized by heating to form an ordered mesoporous carbon film 160 or form factor 170 having domains 180 of ordered pores 190 .
  • the substrate 120 or scaffold 140 can be at least partially volatilized and/or incorporated into the film 160 or form factor 170 .
  • the ordered mesoporous carbon material is formed from a concentrated precursor mixture comprising: i) a water-soluble carbon precursor/H 2 O solution, ii) a non-ionic surfactant, and iii) an oil, which is dried to form a surfactant-based self-assembly in which the surfactant defines, and the cross-linked carbon precursor stabilizes, the mesostructure phase.
  • the mesostructure phase is transformed via the sequential removal of solvent(s) and the surfactant-based template into an ordered mesoporous carbon film or form factor.
  • the ordered mesoporous carbon films and form factors made in accordance with the present invention preferably have oriented, uniform, mesopore diameter (2-50 nm) pores, high surface area, and good mechanical strength.
  • these physical attributes can be controlled by adjusting other process variables such as humidity, pH, drying conditions, cross-linking conditions, heat treating conditions, and the choice of substrate or scaffold.
  • the precursor mixture used to form ordered mesoporous carbon films and form factors includes a carbon precursor/H 2 O, a surfactant, and an oil.
  • a carbon precursor is 510D50 phenolic resin (Georgia Pacific), which comprises two different molecular weight species (GPC data, M n ⁇ 2800 and ⁇ 1060).
  • Additional suitable water-soluble carbon precursors include thermosetting carbohydrates, polyvinylalcohols, resorcinol-formaldehyde, peptide amphiphiles, lipids, and other phenolic resins.
  • Useful surfactants are PEOy-PPOx-PEOy tri-block co-polymers available from BASF, Inc.
  • the surfactant functions as a removable organic template for the carbon precursor.
  • the amount of water and oil that are incorporated into the precursor mixture can be used to manipulate the self-assemblage of the surfactant through its liquid crystal phases and, in turn, the mesoporous structure and properties of the resulting mesoporous carbon material.
  • the chemistry of the precursor mixture can be used to control, for example, the resulting pore diameter and pore volume.
  • the oil acts as a swelling agent for the PPO block.
  • concentration of oil in the precursor mixture can be used to control the swelling of the hydrophobic part of the micelle structure, and can also control the pore size and pore mesostructure of the resulting ordered mesoporous carbons.
  • the addition of oil changes the aqueous mixture from a two phase system to a three phase system. The oil also expands the range of the water, surfactant and carbon precursor compositions within which a particular mesostructure is stable.
  • oils water-immiscible liquids
  • suitable oils water-immiscible liquids
  • p-xylene octane
  • hexadecane hexanol
  • pentanol butyl acetate
  • mesitylene mesitylene
  • the concentration of water in the precursor mixture can be used to control the assemblage of mesoporous channels in both the cross-linked material and in the heat treated (carbonized) product.
  • water interacts with the PEO blocks and, by swelling the phase containing the carbon precursor, can affect the self-assembly of the surfactant template.
  • the carbon precursor:water ratio can be varied over a wide range of compositions.
  • the precursor mixture can have a carbon precursor:water ratio ranging from 5:0 to 1:4 (e.g., 5:0, 4:1, 3:2, 2:3, and 1:4).
  • the PEOx-PPOy-PEOx tri-block co-polymer (e.g., 3.7 g PluronicTM F127) is added to absolute ethanol (18% F127 in 20 ml of ethanol) and stirred with applied heat until the co-polymer is at least partially dissolved in the ethanol.
  • a known quantity of de-ionized water (e.g., 1.4 ml) is added to the mixture, which results in further dissolution of the co-polymer.
  • the phenolic resin (3.0 ml) is added slowly to the mixture followed by vigorous stirring.
  • Butanol (1.5 ml) is then added to the mixture followed by continued stirring to produce precursor mixture A.
  • 5N HCl (0.6 ml) can be added to precursor mixture A to completely dissolve the co-polymer.
  • the precursor mixture is preferably stirred at room temperature for 20-30 minutes prior to use.
  • a preferred method of coating a substrate or scaffold with a precursor mixture is dip-coating.
  • the substrate or scaffold is immersed into a bath of the precursor mixture whereby the precursor mixture forms a layer over exposed surfaces of the substrate or scaffold.
  • coated surfaces include both visible surfaces as well as surfaces within the interior of the scaffold, i.e., surfaces that are coated via infiltration and/or impregnation of the precursor mixture.
  • the step of dip-coating can be repeated, which can result in a thicker coating. Individual dip-coating steps can be performed in succession, or separated by one or more of the step(s) of drying, cross-linking, and heat treating.
  • precursor mixtures can be coated onto substrates or scaffolds by spin coating, spray coating, casting, etc., and then dried, cross-linked and heat treated to form carbon films and form factors.
  • excess precursor mixture can be removed from the substrate or scaffold using a variety of techniques. For example, an elastic foam substrate can be pressed to remove excess precursor.
  • the substrate or scaffold can comprise an organic or an inorganic material, and can be a porous or substantially non-porous material.
  • suitable (porous or non-porous) organic materials include polymer foams, beads, fibers, sheets and coatings, paper, cloth, and other cellulose-based materials.
  • suitable inorganic materials include carbon, glasses, ceramics, semiconductors, and metals.
  • suitable scaffolds can comprise honeycombs, foams, fibers, corrugated sheets or plates, etc.
  • the drying comprises evaporation of the water and other volatile liquids to form an ordered pre-carbonized mesostructure phase.
  • the coated substrate or scaffold is dried at room temperature for a specified time (e.g., 1, 2, 3 or more hours).
  • the ordered pre-carbonized mesostructure phase is defined by a self-assembled surfactant (e.g., tri-block co-polymer) and an at least partially cross-linked carbon precursor (e.g., phenolic resin).
  • the self-assembled surfactant functions as a template that facilitates ordering of the carbon precursor within the pre-carbonized mesostructure phase.
  • the carbon precursor is cross-linked.
  • samples are placed in a desiccator and heated according to the cross-linking cycle disclosed in Table 1.
  • Cross-linking stabilizes the pre-carbonized mesostructure phase.
  • cross-linked membranes Prior to the heat treatment, cross-linked membranes can have a thickness of about 150 to 700 micrometers, which, as disclosed below, are reduced upon carbonization by approximately 20-30%.
  • the cross-linked membrane-coated substrates or scaffolds can be, for example, heated in an oven in a nitrogen atmosphere according to a predetermined heating profile.
  • samples are heated at a first heating rate to 400° C. for 3 hr to volatilize the surfactant, and then heated at a second heating rate to 800° C. for 3 hr to carbonize the carbon precursor.
  • Thermogravimetric analysis data indicates that the surfactant template is decomposed and volatilized at a temperature between 300° C. and 400° C.
  • the first and second heating rates can range from 0.1 to 5° C./min.
  • the first heating rate can be about 2° C./min
  • the second heating rate can be about 1° C./min.
  • a preferred heat treatment step comprises initially heating at 2° C./min to 400° C. for 3 hr, then heating at 1° C./min to 800° C. for 3 hr prior to cooling to room temperature.
  • a majority of the organic scaffold (carbon material) can be incorporated into the reticulated structure of the ordered mesoporous carbon product.
  • the ordered mesoporous carbon material comprises domains of well-aligned mesoscale porosity.
  • the process of forming a carbon film on a substrate or scaffold can result in a post-carbonization pore alignment that is generally perpendicular to the substrate or scaffold surface.
  • a method of forming an ordered mesoporous carbon film further comprises removing the film from the substrate to form a free-standing film.
  • the inventive process can produce carbon material having a higher effectiveness factor than carbon produced by conventional methods.
  • the effectiveness factor relates to the fraction of surface area that is accessible or exposed to reacting or adsorbing species.
  • the inventive ordered mesoporous carbon films and form factors can have an effectiveness factor greater than about 75%.
  • Such structures can perform more effectively as filters or catalyst substrates than conventional carbon powders because of a higher available surface area, and the relative ease and enhanced efficiency associated with incorporating the films and form factors into filter apparatus and reactors.
  • reticulated form factors such as foam blocks, corrugated plates, honeycombs, and interlaced fibers can provide flexible reactor design, easy material loading and unloading, and better temporal control of flow conditions by minimizing clogging and flow pattern disruption.
  • the ordered arrays of pores allow engineers to design reactor geometries that accommodate flow conditions and take advantage of the ordered mesoporous carbon reactive surfaces.
  • Such structures can also improve exposure to reactants and minimize mass transfer limitations.
  • Ordered mesoporous carbon (post-carbonization) films can have a thickness ranging from about 100 to 500 micrometers.
  • the ordered mesoporous carbon material produced via the heat treatment step can optionally be activated in order to increase its available surface area or otherwise enhance its activity.
  • the activation step can also modify the pore size distribution within the ordered mesoporous carbon. For instance, the activation can introduce micro pores ( ⁇ 2 nm) into the mesoporous structure.
  • the activation step can comprise one or more of a thermal activation step or a chemical activation step.
  • the ordered mesoporous carbon material can be activated by heating to an elevated temperature (e.g., 500-1000° C.) in a CO 2 or steam (H 2 O) atmosphere.
  • the structured carbon can be activated via solution redox chemistry using an oxidizing agent.
  • the oxidizing agent can also be used to control the pore size and pore size distribution.
  • the activation partially oxidizes the surface of the carbon material, but advantageously leaves intact the structured array of carbon channels.
  • the activation process also provides active sites for ion exchange with active species or catalysts along the internal surfaces within the channels.
  • the carbon material can be used as an active filter, membrane, or catalyst support.
  • carbon surfaces can, if desired, be chemically functionalized and/or charged by using electrostatics in a post-carbonization step.
  • an ordered mesoporous carbon film was activated and functionalized.
  • a precursor mixture is coated onto at least one of two different substrates, and prior to carbonizing, the substrates are brought together in order to sandwich the deposited layer(s) between the substrates. Subsequent drying, cross-linking, and heat treating of the deposited layer(s) within the substrate/deposited layer(s)/substrate stack can produce a free-standing, ordered mesoporous carbon film.
  • a precursor mixture is dip-coated onto a ceramic honeycomb substrate, dried, cross-linked and heat treated.
  • the carbon film-coated honeycomb substrate is activated by heating in flowing CO 2 /N 2 at 900 ° C.
  • the sample is then immersed into a room temperature solution of HAuCl 4 and urea at pH ⁇ 4, and the solution temperature is raised to ⁇ 80° C. under constant stirring.
  • the increase in temperature induces decomposition of the urea, a concomitant increase in pH, and the precipitation and deposition of fine gold particles on the carbon.
  • a free-standing, ordered mesoporous carbon (OMC) thin film comprises an amorphous carbon network having parallel pores, or channels, that form ordered domains of nanoscale (mesoscale) porosity.
  • Individual pore diameters can range from about 2 to 50 nm, while the length of individual pores can range from about 50 nm to several micrometers.
  • the thickness of the carbon wall that separates adjacent pores can range from about 2 to 10 nm.
  • Ordered mesoporous carbon thin films are capable of chemical activation for ion-exchange and surface adsorption and can have a surface area greater than about 300 m 2 /g.
  • An ordered mesoporous carbon form factor comprises an inorganic scaffold having a coating of ordered mesoporous carbon formed thereon.
  • the inorganic scaffold can have a planar, fibrous, acicular, or tubular structure, and/or can have a reticulated structure, such as a solid foam, honeycomb array, corrugated sheet, etc.
  • the inorganic scaffold can comprise one or more of a glass or crystalline oxide, carbon (e.g., graphite), nitrides, carbides, etc.
  • a preferred inorganic scaffold material adheres the OMC precursor coating and is configured to mechanically and chemically withstand the steps of coating, drying, cross-linking and heat treating to temperatures in excess of 1200° C.
  • a preferred inorganic scaffold material is inert to chemical and thermal decomposition, including melting, and does not undergo uncontrolled or undesired chemical reactions during synthesis of the form factor.
  • an ordered mesoporous carbon form factor is as described above, but comprises an organic scaffold, a first carbon material (derived from the organic scaffold), and a second carbon material (derived from the carbon precursor).
  • the organic scaffold can have a planar, fibrous, acicular, or tubular structure, and/or can have a reticulated structure, such as a solid foam, honeycomb array, corrugated sheet, etc.
  • the organic scaffold can be made of a polymer, such as polyacrylic, polystyrene, or a cellulosic or other organic material, and can comprise organic fibers, including synthetic fibers, that were created into various forms, such as woven fiber fabrics, twine, polymer (plastic) fabrics, polymer foams, sponges, etc.
  • a polymer such as polyacrylic, polystyrene, or a cellulosic or other organic material
  • organic fibers including synthetic fibers, that were created into various forms, such as woven fiber fabrics, twine, polymer (plastic) fabrics, polymer foams, sponges, etc.
  • the organic scaffold preferably adheres the OMC precursor coating throughout the steps of coating, drying, cross-linking and heat treating, and is configured to carbonize within the same temperature regime as the ordered mesoporous carbon precursor while retaining its pre-carbonized structure.
  • the scaffold preferably functions as a structural support for the ordered mesoporous carbon coating.
  • FIG. 2 shows scanning electron micrographs for ordered mesoporous carbon form factors prepared using organic, reticulated scaffolds such as (A) foam, (B) cloth, or (C) paper towel.
  • FIGS. 2(A) and 2(C) each show macroscale images of the foam- and paper-derived ordered mesoporous carbon, and high resolution images of the mesoscale structure.
  • FIG. 2(B) shows high resolution SEM images of the cloth-based ordered mesoporous carbon form factor.
  • the form factors each comprise an ordered mesoporous structure throughout the material, which is retained from the organic template, as well as a macroporous structure corresponding to the starting scaffold.
  • the micrographs are shown in increasing magnification from Roman numeral (I) through (III).
  • Each scaffold was coated by a dip-coating process using precursor mixture A. Excess precursor mixture was removed and each sample was then dried at room temperature overnight. The dried coating was cross-linked by heating according to the schedule disclosed in Table 1, and then heat treated at 900° C. under flowing nitrogen to yield a ordered mesoporous carbon form factor.
  • X-ray diffraction (XRD) data for the carbonized foam and carbonized cloth reveal a hexagonally-ordered pore structure.
  • XRD data was also obtained for powder samples of the ordered mesoporous carbon material.
  • FIG. 3 shows a well-resolved d(100) peak at about 90 ⁇ for both the carbonized foam and carbon powder with two higher order peaks corresponding to d(110) ⁇ 52 ⁇ and d(210) ⁇ 37 ⁇ at 1.7 and 2.4 two-theta, respectively.
  • the XRD intensity for the carbonized cloth is less, which is believed to be due to the relatively low porosity of the material and hence reduced amount of coating.
  • the data show X-ray reflections for (a) powder, (b) carbonized foam, and (c) carbonized cloth samples.
  • FIG. 4 shows scanning electron micrographs for comparative carbon material prepared using a foam scaffold (as in FIG. 1(A) ).
  • precursor mixture A a mixture comprising only the carbon precursor was used.
  • macroporosity from the foam scaffold
  • microporosity 250-350 micrometers
  • the micrographs are shown in increasing magnification from Roman numeral (I) through (II).
  • Precursor mixture A (with and without HCl) was coated onto Pyrex® or aluminum substrates, and the solvent was evaporated overnight at room temperature to produce a viscous, yellow layer.
  • Each layer was cross-linked by heating according to the schedule disclosed in Table 1. The cross-linked films were cut to a specified size, placed between two thick plates and carbonized by heating to a pre-determined temperature prior to cooling to room temperature.
  • the free-standing ordered mesoporous carbon films exhibit a lateral dimensional change (shrinkage) of about 60% and a weight loss of approximately 75%.
  • the normal thickness change (z dimension) is between 20 and 30%.
  • FIGS. 5 and 6 Scanning electron microscopy (SEM) was used to evaluate and measure film geometry, including pore size and orientation. As shown in FIGS. 5 and 6 , the thickness of the films deposited on both Pyrex® and aluminum was approximately 125 micrometers, and each free-standing film comprised an ordered mesoporous structure throughout its thickness with pores oriented substantially parallel to the substrate.
  • FIG. 5A shows a cross-sectional image along a top edge
  • FIG. 5B shows a cross-sectional image along a bottom edge
  • FIG. 5C is a cross-sectional view.
  • the bottom surface texture for the films on Pyrex® substrates was substantially smoother than for films prepared using aluminum substrates.
  • cross-sectional (A), top surface (B) and bottom surface (C) images show some texture and, in some cases, macroporosity.
  • the substrates are identified by reference numerals 200 (Pyrex®) and 300 (aluminum). Divots observed in the bottom surfaces are the footprints of NaCl crystals, and are due to NaCl in the Georgia Pacific resin.
  • FIG. 7 shows X-ray diffraction plots for ordered mesoporous carbon powder and a free-standing film showing reflections for (a) powder, (b) film top surface, and (c) film bottom surface.
  • X-ray diffraction data for the free-standing carbon films reveal a hexagonal ordering of the pore structure at both the top and the bottom surface of each film. The hexagonal ordering is also observed in the powder sample. Top and bottom surfaces have well-resolved d(100) reflections at 77 ⁇ (top) and 72 ⁇ (bottom), and higher order d(200) peaks at ⁇ 42 ⁇ (top) and 38 ⁇ (bottom).
  • the powder sample displays a well-resolved d(100) peak at 86.5 ⁇ with a higher order d(110) peak at ⁇ 50.2 ⁇ .
  • the free-standing films typically exhibit reflections shifted to lower d-spacings suggesting that some compaction takes place during film formation.
  • Pore volume distribution (PVD) data were obtained by breaking individual free-standing films into smaller pieces.
  • the pore size varies from 2-7 nm with a relatively narrow distribution.
  • the surface area for non-activated samples ranges from about 450-600 m 2 /g, while the surface area for activated samples ranges from about 1000-1800 m 2 /g.
  • Mercury porosimetry results show that non-activated films comprise from 60-70% porosity, and that the porosity can be increased to values in excess of 70% by including HCl in the precursor mixture.
  • the resistivity measurements comprise applying silver conductive paint to the carbon films to form electrodes, attaching silver wires to the electrodes, measuring resistance with a digital multimeter (4-wire configuration), and calculating the resistivity from the measured resistances using the sample and electrode geometries.
  • Table 3 shows resistivity and conductivity data for both in-plane and through-plane measurements for samples 1-9.
  • the pH of the precursor mixture in samples 1-9 was varied by controlling the amount of hydrochloric acid used. Though not measured, the pH for samples 1-5 was believed to be in the range of about 1-2.
  • Sample 6 had a pH of 0.96 with a standard deviation of 0.2.
  • Sample 7 was made with no HCl, and had a pH of 8.5 with a standard deviation of 0.2.
  • the pH for samples 8 and 9 was 8.37 and 8.33, respectively.
  • Samples 1-4 and 6-9 were heat treated at 900° C., while sample 5 was heat treated at 1200° C.
  • the resistance increases with increasing film thickness.
  • the in-plane resistivity decreases substantially by increasing the heat treating temperature from 900° C. to 1200° C. (sample 5).

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CN103189131A (zh) * 2010-08-06 2013-07-03 台达电子工业股份有限公司 多孔材料的制造方法
US10287412B2 (en) 2012-10-18 2019-05-14 Cic Energigune Process for the preparation of hierarchically meso and macroporous structured materials
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CN113603077A (zh) * 2021-08-23 2021-11-05 绍兴海崐新材料科技有限公司 一种高吸附力球形介孔碳的制备方法

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